Manifolding transfer and method of making



Sept. 22, 1953 J. G. ZIMMERMAN ,653,

MANIFOLDING TRANSFER AND METHOD OF MAKING- Filed March 17, 1948 INVENTOR. JEROME G. ZIMMERMAN Y iw mw ATTWORNEY Patented Sept. 22, 1953 ,MANIFOLDING TRANSFER AND METHOD OFMAKI Jerome .G- Zimmerman, West Milton, Ohio, 215 .signor to The StandardRegister Qoni'pany l lii fa.. r c p c W Application March 17, 1948, Serial No. 15,503

i inal h g 9 typ n rep od ogsi on a copy placed beneath the original i sheet, such copies are coloring matter fro a tr H either on the back fof the; iginalflor duplicatin sheets to an adjacent sheet or onto 'separate interleaved sheets. It is an object of the present invention to provide a method of manifolding and the means whereby the use of "carbon black or other darl; coloring matter transfer surfaces with their" attendant d adv ta es- .dis ensedwi "It is an object of: thepresient invention to provide a writing sheetvvhos trans-fer surface on the rear thereof has heretn'twc compounds'capa'ble of reacting withieach 'other to" form a dark colored sulfide und'er'difierent conditions than those existing. The coating must'be ic'a'pableof transfer to a contiguous paper surface at the points of impression'up'on the reverse side of the impacted sheet.

It is more particularly an object to provide writing sheets whose transter surfaces on the rear thereof havea colorless or light colored, substantially solid coating containing b'othfa lead compound anda sulfide compound but 'which'are prevented from reacting' by the presence of a sufficient amount of an acidic manganese salt to maintain an acidic condition in the coating. Yet if this acidic condition were neutralized by'gas'eousammonia the dark coloredlead sulfide "would result.

It is more specifically an object of this present invention to transfer from the transfer surface (rear surface or overlying sheet) onto thecopy sheet .(frontsurface ,of contiguous sheet below) colorless 'or'light' colored characters are duplicates. of those formed upon the original sheet in a typing or writing operation, and then treat the copysheet'havingtheimprin color less or substantially colorless charact ing the'two aforesaid designated components with gaseous "a'mmoni easily legible dark colored characters. Th exposure of the colorless characters to the anhydr us. ammo -.i I; iallcw the. color le a tr e nt-to reactnormally t? the tr inierf e 91 ns coat n .ca ri 9 QQQXSSFm.

a transfer surface or writing paper hav' and inherentmeri M in mentionedl I i r r With the ammoniumagtqta imiilsaial objectsin view as will more fully appear in the 1 ification, the invent on ten d' be p otected by Letters ,Patentbonsists of the advantagebujsfeatures, thecomponents of the coating composition, and the mo de of application and use a'shereinafter described or illustrated in the accompanying 1 drawing, or their equivalents.

jln' t l' ea 'ccompany ing drawing, which is of a diagrammatic nature,

Fig: 1"is a view of a single sheet of writing paper with the transfer surface or coating applied Eiggg is a View of an assembly of superposed writng shefetsibrrriing afset' of manifold record J '7 I s Fig.3 is a view similar to Fig. 1, but showing aslightly rnodified' form 'ofthe invention, and Fig; 4is awiewlof -ar'i a'-'s"sen b1y of superposed writing sheetsf'o'rniinga 'et of manifold record forms, the sheets-being'producedin accordance withfthejdisclosure' of Fig.3.

1 fLikeparts are'indicat'ed by similar characters of" reference throughout the several views.

' ficcordjingftothe 'present invention the set of manifold "material comprises a series of two or more s'izedsheets l flf oh'the rear surface of each sheet of which series'(except the bottom sheet if this is undesirable) there'i's provided a substantially solid,"uniform,colorless or very light colored coating H confining a metallic compound, whiic fi'is capablef ifo'rrninga dark colored sulfi'de precipitate with the c'o-existing water-soluble colorless sul ide" but for the presence of the acidic manganese I salt" creating 1 an acidic condition. This; coating must be" transferable from the rear surface at points of im'pacthpon theoriginal sheet to the top surface of a contiguous paper s'urf'acein orderto duplicate the imprinted characters. JJTh'ere fis jno'reason actually for having the rearsurface ofthebottoni sheet contain any coating. ,Thefltransfefletters, figures, etc. are

thencausedztdbecome legible. bytreatingthe copy sheets with .tanhydrous ammonia, i. e. NH3 in the gaseous staterv- The explanation of the/formation ,of the dark colored,xlegibletcharacters is;due to. the ammonia neutralizing ;the' .acidic manganese salt, such as manganous nitrate; whereby .the water-soluble 3 an emulsion i I containing a water-soluble sulfide and the metallic compound capable of reacting therewith to form a dark colored, insoluble sulfide but for the presence also of an acidic inanganese salt which is present in an amount sufii cient to create an acidic condition; this composition must be capable of drying to a fairly solid condition or state after its application. A

satisfactory coating composition is an emulsion containing a volatile organic liquid, water, av

water-soluble lead compound, an alkali metal sulfide, an acidic manganous salt and a polyvalent metal salt of a higher fatty acid the sulfide of the metal of which is colorless. Each of these components must be colorless or possess a light color.

It is preferred however to coat the sized sheets of paper H! with an emulsion 12 containing the alkali metal sulfide, a volatile organic liquid and water, then after this coating has dried apply an emulsion l3 containing the watersoluble lead salt, a volatile organic liquid and water. In both emulsions a polyvalent metal salt of a higher carboxylic acid, the sulfide of the metal of which is colorless, more particularly an aluminum salt of a higher fatty acid, such as aluminum palmitate may be used. The organic liquid phase in each can be the same, but this is a matter of convenience.

The water-immiscible liquid for the emulsion or emulsions may be any suitable, volatile organic liquid such as carbon tetrachloride, benzene, toluene, etc. The polyvalent metal salt of the higher carboxylic acids may be those of aluminum, calcium or zinc. It is preferred to use aluminum stearate or the aluminum salts of other hi her fatty acids; but the aforesaid metallic salts of naphthenic or the resin acids may be used. Water-soluble lead salts giving the best results are lead nitrate or the basic acetate. When the lead salts of the higher fatty acids are employed, such as lead palmitate, it is unnecessary to employ aluminum palmitate with lead nitrate or basic lead acetate. Sodium or potassium sulfides are suitable water soluble sulfides. v V Y Bleached shellac may be added to the emulsion to alter the color and improve the texture of the coating for some varieties of paper. The more bleached shellac present, the lighter the color will be. But too much will hinder the reaction. Amounts of 1-10% based on the total weight of the coating composition are usually suitable. Instead of bleached shellac other light colored natural or synthetic resins which dry to a fairly solid state can be employed. 7

The emulsions or dispersions herein described may be applied to various weights and qualities of sized paper having a surface which will take and hold the coatings. They may be app-lied in any suitable manner, such as spraying, brushing and various coating methods. The thickness will be governed partly by economic consideration but an even thin coating should be secured. V

For a fuller understandin of the nature and objects of the invention, reference should be had to the following examples which aregiven merely to illustrate the invention and are not to be construed in a limiting sense, all parts being given by weight:

EXAMPLE 1 Emulsion No. 1

. Parts by Weight Manganese nitrate (70% solution) 3 Potassium sulfide 2 Carbon tetrachloride 140 Aluminum palmitate 5 Water These ingredients were well mixed and the resulting emulsion I2 was applied to the rear surface of the selected, sized paper. Then after drying, emulsion it formed from the following components was applied to the thus coated paper:

Emulsion N0. 2

Parts by weight Lead nitrate 6 Carbon tetrachloride 150 Aluminum palmitate 6 1 Water 20 the top sheet which carried the original, were then exposed to dry ammonia gas (NEE) containing a trace of hydrogen sulfide, such as 1%. The latter is not necessary but its use accelerates the reaction. As a result the previously practically invisible characters and figures became legible; they turned a semi-black color, and were clear, distinct and non-smudging. The explanation is that whereas in an acidic environment due to the presence of the acidic manganous nitrate the black lead sulfide is incapable of formin yet in a neutralized medium it is capable.

In the above example bleached shellac can be used, being substituted up to 10% based on the total percent for the corresponding ratios of the other components.

EXAMPLE 2 An emulsion for applying as the second coating in the preferred method of securing a manifold sheet can be formed from-the following composition: I

Percent Carbon tetrachloride 74.2 Aluminum palmitate 2.45 Silver nitrate 1.65 Manganese nitrate 1.90 Shellac solution (55.6% alcohol) 3.30 Vfater 16.5

In other formulae, shellac Was used without alcohol:

, Parts by weight Carbon tetratchloride 3 Aluminum chloride 5 Silver nitrate 4 Manganese nitrate 4.6 Shellac (solid) 10 Water 3O Manganese sulfate may also be used instead of the nitrate. It will be understood that an emulsion containing an alkali metal sulfide (Emulsion No. 1 type in Example 1)'is applied to the sized paper first and dried before the emulsion containing the silver nitrate is applied and the treated paper again permitted to dry.

It will 7 be understood that, whereas certain specific examples have been described in the foreclaims the term colorless is used to embrace light colored shades as well as white. In. both the specification and claims the termhigher carboxylic acids or highercarboxylateradical denotes any carboxylic acid of eight or more.

carbon atoms and preferably twelve or more. Where higher fatty acids are referred to there is meant the long chain carboxylic acids nor-. mally present as glycerides in fatty oils, and fats.

While specific materials, and proportions-have been described herein, it will'beunderstood that various changes andfmodificationsmay be made without departing from the spirit and scope of the invention. Accordingly I-donotintend that my invention shall be limited tosuch embodiments and examples, except as hereinafter described in the appended claims.

I claim:

1. In manifolding, a sheet of sized paperon one side of which is a substantially uniform, firm, nonsticky, non-tacky, colorless coating containing a water-soluble sulfide, an acidic manganese salt in an amount sufiicientto produce an acidiccondition in the coating awet condition; said coat ing being characterized by the presence of a higher carocxylic acid radical in the form of a water-insoluble salt, and' a, metallic element of a salt, the said metallic element-being capable of forming dark colored Water-insolublesulfide with the aforesaid water-soluble sulfide but for the presence of said manganese salt, and said coating being further characterized in that when said metallic element is combined as a salt which is water-soluble, the said carboxylic acid radical is combined as a salt of a polyvalent metal the sulfide of which is colorless.

2. A coated sheet of sized paper set out in claim 1 wherein the said water-soluble sulfide and the said metallic compound are present in the ratio of their chemical equivalents.

3. In manifolding, a sheet of sized paper on one side of which is a substantially uniform, firm, non-sticky, non-tacky, colorless coating containing an alkali metal sulfide, an acidic manganese salt in an amount sufiicient to produce an acidic condition in the coating said coating being characterized by the presence of a higher carboxylic acid radical in the form of a water-insoluble salt, and a lead element of a salt, the said lead element being capable of forming dark colored water-insoluble sulfide with the aforesaid watersoluble sulfide but for the presence of said manganese salt, and said coating being further characterized in that when said lead element is combined as a salt which is water-soluble, the said carboxylic acid radical is combined as a salt of a polyvalent metal the sulfide of which is colorless.

4. A coated sheet of sized paper set out in claim 3 wherein the said alkali metal sulfide and the said lead compound are present in the ratio of their chemical equivalents.

5..In the process of producing a manifolding sheet the steps of coating a surface of a sized sheet of paper with a colorless emulsion of water, a water-immiscible volatile organic liquid, an alkali metal sulfide, an acidic manganese salt in an amount sufiicient'to produce an acidic condition, saideiniilsionbeing characterized by the presence of a. higher carboxylic acid radical in;

the form of a water-insoluble. salt, and a. metallic element of a salt, the said. metallic element being capable of forming dark colored water-insoluble sulfide with the aforesaid watersoluble sulfide but for the presence of, said manganese salt, and said coatingzbeing further char-- acterized in that when said metallic. element is combined as a salt which is water-soluble, the said carboxylic acid radical is combined as. a salt of a polyvalent metal the sulfide of which is colorless.

6. The emulsion set out in claim 5 wherein said alkali metal sulfide and the said metallic compound arepresent inthe ratioof their chemical equivalents.

'7. The emulsion set'out'in claim 5 wherein lead is the metallic compound capable of forming the dark colored sulfide.

8. In the process of producing manifolding sheets the steps of coating a surface of sized sheets Of paper with a colorless emulsion containing water, water-immiscible volatile organic liquid, a polyvalent'metal salt of a higher car-'- boxylic acid the metallic sulfide of the metal of which is colorless, an alkali metal sulfide and. an acidic manganese salt which'latter salt is present in an amount suflicient to produce an. acidic condition in the emulsion, permitting the emulsion coat to dry, then coating-the same.sur,-- face with an emulsion containing water, a W34? oer-immiscible volatile organic. liquid, at. poly-- valent metal salt of a higher carboxylic acid, the metallic sulfide of themetal of which is colorless, and a water-soluble salt ofa metal capable of forming a dark-colored sulfidewith. the alkali metal sulfide, when the acidic condition is neutralized, and thereafter causing the coated sheet to dry.

9. The process of making copy comprising imprinting legible characters upon the top surface of a sized paper sheet upon the rear surface of which is a substantially uniform, firm, nonsticky, non-tacky, colorless coating containing an alkali metal sulfide, an acidic manganese salt in an amount sufficient to produce an acidic condition in the coating in a moist condition said emulsion being characterized by the presence of a higher carboxylic acid radical in the form of a water-insoluble salt, and a metallic element of a salt, the said metallic element being capable of forming dark colored water-insoluble sulfide with the aforesaid water-soluble sulfide but for the presence of said manganese salt, and said coating being further characterized in that when said metallic element is combined as a salt which is water-soluble, the said carbo-xylic acid radical is combined as a salt of a polyvalent metal the sulfide of which is colorless, thus transferring these characters to a sheet below this coated sheet, then treating this sheet with dry ammonia gas to cause the transferred characters to become dark and legible.

10. In the process of producing manifold sheets the steps of coating a surface of sized sheets of paper with a colorless emulsion containing water, a water-immiscible, volatile organic liquid, a polyvalent metal salt of a higher carboxylic acid, the metallic sulfide of the metal of which is colorless, an alkali metal sulfide and an acidic manganese salt, which latter compound is present in an amount sufficient to produce an acidic condition in the emulsion, thereafter causing the coated sheets to dry, then coating the same surface with an emulsion containing water, a waterimmiscible volatile organic liquid and a salt of a higher carboxylic acid with a metal whose sulfide is dark colored, and thereafter causing the treated sheet to dry.

11. The process of making copy comprising imprinting legible characters upon the top surface of a size paper sheet upon the rear of which there are two superimposed substantially uniform and solid coatings one of which contains an alkali metal sulfide, a polyvalent metal salt of a higher carboxylic acid, the sulfide of the metal of which is colorless, and an acidic manganese salt, in an amount sufiicient to produce an acidic condition in the coating the other of which coating contains a water-soluble lead salt and a polyvalent metal salt of a higher carboxylic acid, the sulfide of the metal of which salt is colorless, thus transferring these characters to a sheet below this coated sheet, then treating that sheet with dry ammonia gas to cause the transferred characters to become dark and legible.

12. The process of making copy comprising imprinting legible characters upon the top surface of a sized paper sheet upon the rear of which there are two superimposed substantially uniform and solid coatings one of which contains an alkali metal sulfide, a polyvalent metal salt of a higher carboxylic acid, the sulfide of the metal of which is colorless, and an acidic manganese salt in an amount sufiicient to produce an acidic condition in the coating, the other of which coating contains a lead salt of a higher carboxylic acid, thus transferring these characters to a sheet below this coated sheet, then treating that sheet with dry ammonia gas to cause the transferred characters to become dark and legible.

13. In manifolding, a sheet of sized paper on one side of which are two superimposed substantially uniform, solid coatings one of which contains an alkali metal sulfide, a polyvalent metal salt of a higher oarboxylic acid, the sulfide of the metal of which is colorless, and an acidic manganese salt in an amount suificient to produce on acidic condition in the coating, the other of which coating contains, a water-soluble lead salt and a polyv-alent metal salt of a higher carboxylic acid, the sulfide of the metal of which salt is colorless.

14. In manifolding, a sheet of sized paper on one side of which are two superimposed substantially uniform, solid coatings one of which contains an alkali metal sulfide, a polyvalvent metal salt of a higher carboxylic acid, the sulfide of the metal of which is colorless, and an acidic manganese salt in an amount sufiicient to produce an acidic condition in the coating, the other of which coating contains a lead salt of a higher carboxylic acid.

15. The process of producing manifold sheets set out in claim 8, wherein the last two mentioned groups of metallic compounds are present in the ratio of their chemical equivalents.

J EROME' G. v ZIMMERMAN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,950,982 G ookin et al Mar. 13, 1934 2,083,206 Schoeller June 8, 1937 2,188,599 Bjorksten et al. Jan. 39, 1940 2,322,367 Kjellstrand June 22, 1943 

1. IN MAINFOLDING, A SHEET OF SIZED PAPER ON ONE SIDE OF WHICH IS A SUBSTANTIALLY UNIFORM, FIRM, NONSTICKY, NON-TACKY, COLORLESSCOATING CONTAINING A WATER-SOLUBLE SULFIDE, AN ACIDIC MANGANESE SALT IN AN AMOUNT SUFFICIENT TO PRODUCE AN ACIDIC CONDITION IN THE COATING IN A WET CONDITION, SAID COAT ING BEING CHARACTERIZED BY THE PRESENCE OF A HIGHER CARBOXYLIC ACID RADICAL IN THE FORM OF A WATER-INSOLUBLE SALT, AND A METALLIC ELEMENT OF A SALT, THE SAID METALLIC ELEMENT BEING CAPABLE OF FORMING DARK COLORED WATER-INSOLUBLE SULFIDE WITH THE AFORESAID WATER-SOLUBLE SULFIDE BUT FOR THE PRESENCE OF SAID MANGANESE SALT, AND SAID COATING BEING FURTHER CHARACTERIZED IN THAT WHEN SAID METALLIC ELEMENT IS COMBINED AS A SALT WHICH IS WATER-SOLUBLE, THE SAID CARBOXYLIC ACID RADICAL IS COMBINED AS A SALT OF A POLYVALENT METAL THE SULFIDE OF WHICH IS COLORLESS. 